Enhancement of Ethane Selectivity in Ethane–Ethylene Mixtures by Perfluoro Groups in Zr-Based Metal-Organic Frameworks

• Published in: ACS applied materials & interfaces Vol. 11; no. 30; pp. 27410 - 27421
• Main Authors: Pires, João, Fernandes, Joana, Dedecker, Kevin, Gomes, José R. B, Pérez-Sánchez, Germán, Nouar, Farid, Serre, Christian, Pinto, Moisés L
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 31.07.2019; Washington, D.C. : American Chemical Society
• Subjects: Chemical Sciences; gas adsorption; gas separation; simulation; ethane/ethylene separation; metal-organic frameworks
• ISSN: 1944-8244; 1944-8252
• DOI: 10.1021/acsami.9b07115

A series of zirconium dicarboxylate-based metal-organic frameworks (Zr MOFs) of the UiO-66 (tetrahedral and octahedral cages) or MIL-140 (triangular channels) structure type were investigated for the separation of ethane/ethylene mixtures. The adsorption, investigated both experimentally and computationally, revealed that the size and type of pores have a more pronounced effect on the selectivity than the aromaticity of the linker. The increase in pore size when changing from benzene to naphthalene (NDC) dicarboxylate ligand makes UiO-NDC less selective (1.3–1.4) than UiO-66 (1.75–1.9) within the pressure range (100–1000 kPa), while the three-dimensional (3D) pores of the UiOs favor the adsorption of ethane due to the interactions between ethane with more spacers than in the case of the 1D channels of MIL-140s. The impact of the functionalization revealed a very interesting increase of selectivity when two perfluoro groups are present on the aromatic ring (UiO-66-2CF3) (value of 2.5 up to 1000 kPa). Indeed, UiO-66-2CF3 revealed a unique combination of selectivity and working capacity at high pressures. This is due to a complex adsorption mechanism involving a different distribution of the guest molecules in the different cages associated with changes in the ligand/perfluoro orientation when the pressure increases, favoring the ethane adsorption at high pressures.